Structural dependence of the efficiency of functionalization of silica-coated FeOx magnetic nanoparticles studied by ATR-IR

The efficiency of propylamino functionalization of magnetic silica-coated FeO_x nanoparticles prepared by different methods, including coprecipitation and flame aerosol synthesis, has been evaluated by attenuated total reflection infrared spectroscopy (ATR-IR) combined with a specific surface reaction, thus revealing the availability of the grafted functional groups. Large differences in the population of reactive groups were observed for the investigated materials, underlining the tight relation between the structure of nanoparticles and their suitability for organic functionalization. The materials possessed different core structure, surface area, and porosity, as evidenced by transmission electron microscopy and nitrogen adsorption-desorption isotherms. Grafting of aminopropyl groups using a standard procedure based on reaction with (3-aminopropyl)trimethoxysilane as source of the propylamino groups was performed, followed by classical dry analysis methods to determine the specific concentration of the organic functional groups (in mmol g⁻¹ of material). ATR-IR spectroscopy in a specially constructed reactor cell was applied as wet methodology to determine the chemically available amount of such functional groups, showing that the materials possess largely different loading capacity, with a variability of up to 70% in the chemical availability of the organic functional group. The amount of (3-aminopropyl)trimethoxysilane used for functionalization was optimized, thus reaching a saturation limit characteristic of the material.     

High-pressure Fourier transform micro-Raman spectroscopic investigation of diiodine-heterocyclic thioamide adducts

The pressure dependences of the Fourier transform micro-Raman spectra of four heterocyclic thioamides [[(bztzdtH)I2] x I2] (1) (bztzdtH = benzothiazole-2-thione), [(bztzdtH)I2] (2), [[(tzdtH)2I+] x I3- x 2I2] (3) (tzdtH = thiazoline-2-thione), and [[(bzimtH)I2]2 x I2 x 2H2O] (4) (bzimtH = benzimidazole-2-thione) have been studied between ambient pressure and 50 kbar. For 1, generation of I3- ions through disproportionation reactions is evident as the pressure is increased. There are empirical linear correlations between the frequency and (I-I) bond length and the applied pressure. The iodine adduct of thioamide 2 is more sensitive to pressure when compared to the 1 or 4 iodine adducts. This difference in behavior may be attributed to differences in crystal structures or to a lower I-I bond order. Monitoring of other vibrational transitions of the thiomide structure reveals several less important pressure dependences.     

On the importance of zero-point effects in molecular level classical simulations of water

We discuss the fundamental difficulties involved in comparing energetic results obtained via classical simulations of bulk water with the observed values. Emphasis is placed on the difference between quantum and classical dynamics, and correction techniques, which can be used to emulate quantum effects in a classical system, are investigated. We present molecular dynamics simulation results for liquid water using the ‘Thole-type’ all atom polarizable water model, which has previously been shown to give reasonable results for both ice Ih and small water clusters. We employ expressions for the density of states power spectrum in the liquid in either atomic or rigid-body coordinates that are appropriate for rigid molecule simulations. It is demonstrated that the atomic power spectra can be written as a linear combination of the center of mass and rotational power spectra via the use of the ‘coupling matrix’ of linear coefficients. This approach allows us to introduce the concept of ‘fractional degrees of freedom’ (DOF) for nuclei in rigid molecule simulation. Within this framework, it is illustrated that in a rigid water molecule the oxygen and hydrogen atoms have 2.82 and 1.59 DOF, respectively (for the TIP4P geometry). Within our suggested approach, we finally demonstrate that Debye–Waller factors can be obtained from the coupling matrix and show that quantum corrections to the structure can be accounted for by raising the temperature of the system in a classical simulation by approximately 50°, a result consistent with previous suggestions.     

Differential evolution for sequencing and scheduling optimization

This paper presents a stochastic method based on the differential evolution (DE) algorithm to address a wide range of sequencing and scheduling optimization problems. DE is a simple yet effective adaptive scheme developed for global optimization over continuous spaces. In spite of its simplicity and effectiveness the application of DE on combinatorial optimization problems with discrete decision variables is still unusual. A novel solution encoding mechanism is introduced for handling discrete variables in the context of DE and its performance is evaluated over a plethora of public benchmarks problems for three well-known NP-hard scheduling problems. Extended comparisons with the well-known random-keys encoding scheme showed a substantially higher performance for the proposed. Furthermore, a simple slight modification in the acceptance rule of the original DE algorithm is introduced resulting to a more robust optimizer over discrete spaces than the original DE.     

A STUDY OF A FULLY COUPLED TWO-PARAMETER SYSTEM OF SEQUENTIAL FRACTIONAL INTEGRO-DIFFERENTIAL EQUATIONS WITH NONLOCAL INTEGRO-MULTIPOINT BOUNDARY CONDITIONS

In this article, we discuss the existence and uniqueness of solutions for a coupled two-parameter system of sequential fractional integro-differential equations supplemented with nonlocal integro-multipoint boundary conditions. The standard tools of the fixed-point theory are employed to obtain the main results. We emphasize that our results are not only new in the given configuration, but also correspond to several new special cases for specific values of the parameters involved in the problem at hand.     

Partial backlogging inventory lot-size models for deteriorating items with fluctuating demand under inflation

In this paper, the traditional inventory lot-size model is extended to allow not only for general partial backlogging rate but also for inflation. The assumptions of equal cycle length and constant shortage length imposed in the model developed by Moon et al. [Moon, I., Giri, B.C., Ko, B., 2005. Economic order quantity models for ameliorating/deteriorating items under inflation and time discounting, European Journal of Operational Research 162(3), 773–785] are also relaxed. For any given number of replenishment cycles the existence of a unique optimal replenishment schedule is proved and further the convexity of the total cost function of the inventory system in the number of replenishments is established. The theoretical results here amend those in Yang et al. [Yang, H.L., Teng, J.T., Chern, M.S., 2001. Deterministic inventory lot-size models under inflation with shortages and deterioration for fluctuating demand, Naval Research Logistics 48(2), 144–158] and provide the solution to those two counterexamples by Skouri and Papachristos [Skouri, K., Papachristos, S., 2002. Note on “deterministic inventory lot-size models under inflation with shortages and deterioration for fluctuating demand” by Yang et al. Naval Research Logistics 49(5), 527–529.]. Finally we propose an algorithm to find the solution, and obtain some managerial results by using sensitivity analyses.